Reaction products of 2-methyl-1, 3-dichloropropane and alcohols



Patented Feb. '28, 1939 UNITED s'r 'rEs PATENT OFFICE REACTION rnonuors or ammumcnnonornorm AND ALoonoLs Gerald H. Coleman and Garnett V. Moore, Midland, Michu assignors Michigan I to The Dow Chemical ompany, Midland, Mich, a corporation oi No Drawing.- Original application November 20,

1930, Serial No. 111,906. Divided and this application January 10', 1938, Serial No. 184,245

I I 13 Claims. This invention concerns new organic ether products and a method for preparing the same.

We have discovered that when an alcohol is reacted with 2-methyl-1,3-dichlor0propane in the presence of a suitable basic material, useful liquid ether products are formed. We have prepared various ethers according to-the above method, determined certain of their physical properties v whereby they can be readily identified, and have found them useful as general solvents, extractants, plasticizers, and intermediates for the preparation of complex organic, compounds.

In carrying out our invention, an alcohol, 2-methyl-1,3-dichloropropane, and asuitable basic material such as sodium hydroxide are maintained at a, reaction temperature until the I desired conversion is obtained. Sodium chloride termed during the reaction is separated from the reacted mixture, which is-thereaiter fractionall-y distilled to obtain the desired ether products.

The reaction temperature varies with the particu-I' 1 18.1 reactants employed andthe proportions there of present, but, it is generally between about "75 C. and the decomposition temperature of the mixture. The time required for carrying out the process is dependent upon the reactants employed, the temperature of the reaction, and the type oi ether'product desired, substantial quantitles of ether products being generally formed after about 1 to 12 hours of heating at reaction temperature. The process may be conveniently carried out at atmospheric pressure, and when an excess of a lower boiling alcohol is employed in the reaction, at thereilux temperature of the mixture. If desired, however, elevated pressures and temperatures maybe employed. 9

Regardless of the proportions of thereactants employed and the temperatures and pressures under which they are maintained, 3 types of ether products are formed in the above described procedure. The following equation shows a reaction of Z-methyl-1,3-dich1oi'opropane with normal' propane] and is illustrative of the course of the 1 reaction. and the type oi compounds obtained 1,3-dichloro-propa Formula I above is the normal propyl ether of f 2-methyl-3-hydroxy-propene-1; II is the normal propyl ether of 2-methyl-3-chloro-propanol-1; and III is the di-propyl ether'of z-methyl-propandiol- 1,3. The amounts of the above products formed in the reaction vary with time and temperature of reaction and the proportions of re actants employed.

. The followingexamples are illustrative of the procedure followed and the products obtained thereby but are not to be construed as limiting the invention:

5 Example 1 12705grams mols) oi 2-methy1- 1,3-dichloropropane, 800 grams mols) -01 methyl alcohol, and 800 grams (20 mols) or sodium hydroxide were mixed together and maintained at the re-v fluxing temperature of the mixture, 1. e. 7'7-89 C., for a period of 2 hours.;; The reaction mixture was then washed with 3 liters of water to dissolve out sodium chloride iormed in the reaction, and

the oil layer separated and fractionally distilled,

2J-methy1-3-hydroxy-propene-1 was-found to be a free-flowing water-white liquid boiling at 67 0., and having a specific gravity or 0.793 at 20/4 C. The methyl ether of 2-methyI-3-chloropropanel-1 is a water-white liquid boiling at 123-124 C. and having a speciflc'gravity of 0.982 at 20/4 C. The higher boiling fraction containing the di-methyl ether of 2-methyl-propandim- 1,3v was not purified.

' v Emmple 2 7 A mixture of 127- grams (1 mol) of 2-1nethylgrams (2.25 mols) of sodium-hydroxide and 150 grams (2.5 mols) of normal propifiiol was heated to C. and

Winder the. vapor-pressure oi thereactants for 8 hours in a high press'ure rocker bomb. The reaction mixture wasthen washed. with water and 2 distilled, whereby there was obtained '35 grams '(0.304 mol) of the normal propyl ether of 2-methy-3-hydroxy-propene-1, which is a compound boiling at 1l2-114 C., and having a specific gravity of 0.798 at 20/4 C.; 23 grams (0.153 mol) of the normal propyl ether 01' 2-methyl-3-chloropropanol-1, which boils at 97-100 C. at 100 millimeters pressure, and has a specific gravity of 0.964 at 20/4 C.; and 28 grams (0.161 mol) of the dinormal-propyl ether of 2-methyl-propandiol-l,3, which boils between 111 C. and 113 C. at 54 millimeters pressure,

and has a specific gravity of 0.855 at 20/4 C.

2 grams of an ethyl cellulose product having a 48.8% ethoxy content and a viscosity of 17 centipolses was contacted with a mixture or 18 grams of the di-normal-propyl ether of 2-methylpropandiol-1,3 and 5 grams of ethyl alcohol. The resulting clear solution was free from gels, of

medium viscosity, and well for use in film formation.

Example 3 A reaction mixture identical with that disclosed in Example 2 was refluxed for 8 hours at a temperature of 83.5-85 C., and salt subsequently removed from the reaction product by washing with water. .There was obtained 65 grams (0.565 mol) of normal-propyl etherof 2- methyl-3-hydroxy-propene-l; 15 grams (0.1 mol) of normal-propyl ether of 2-methyl-3-chloropropanol-l; and 25 grams (0.144 mol) of the dinormal-propyl ether oi 2-methyl-propandiol-1,3.

Example 4 A mixture consisting oi 254 -(2 mols) of 2-methyl-1,3-dichloro-propane, 245 grams (4 .mols) 01' 98% isopropyl alcohol, and 200 grams (5 mols) of sodium hydroxide was heated to 125 C. and under the vapor pressure of the reaction mixture for a period of 5 hours in a high pressure rocker bomb. The product was thereafter washed from the bomb, filtered, and the A mixture 01 127 grams (1 mol) oi 2-methyl- 1,3-dlchloro-propane, 90 grams (2.25 mols) of sodium hydroxide, and 185 grams (2.5 mols) of normal butyl alcohol was refluxed for 8 hours at a temperature of 109-112 C. The product was washed with water, dried, and distilled whereby there was obtained 13 grams (0.1 mol) of the normal butyl ether of- 2-methyl-3-hydroxypropene-l, which boils at 60-85 C. at 50 millimeters pressure; 40 grams (0.243 mol) of the normal butyl ether 01' 2-methyl-3-chloro-propanol-l which is a water-white liquid boiling at 100-102 C. at 50 millimeters pressure, and having a specific gravity or 0.944 at 20/4 C.; and 35.5 grams (0.178 mol) of di-normal butyl ether 01' 2-methyl-propandiol-L3, which boils at' 139.5"-

\ 142 C. at 50 millimeters pressure, and has a specific gravity or 0.856 at 20/4 C.-

Example 6 i In'asimilarmanner127gmms(1'mol)oi'2- -methyl-1,3-dichloro-propane, grams (2.25

mols) of sodium hydroxide, and 255 grams (2.5 mols) of normal hexyl alcohol were refluxed for 8 hours at a temperature of 124-127 C. The

. reaction product was washed with water, dried,

and distilled, whereby there was obtained 10 grams (0.064 mol) oi the normal hexyl ether of 2-methyl-3-hydroxy-propene-1, boiling between and 120 C. at 60 millimeters pressure; 42 grams (0.218 mol) of the normal hexyl ether of 2-methyl-3-chloro-propanol-1, ,a water-white compound boiling at l32-l33 C. at 50 millimeters pressure, and having a specific gravity of 0.927 at 20/4 C.; and 44 grams (0.171 mol) of di-nor'mal hexyl ether of 2-methyl-propandiol- 1,3, which bolls at 140141 C. at 6 millimeters pressure, and has a specific gravity of 0.857 at 20/4 C.

Example 7 127 grams (1 mol) of 2-methyl-1,3-dichloropropane, 90 grams (2.25 mols) of sodium hydroxide, and 250 grams I hexanol were mixed together and refluxed at 126-l29 C. for 8 hours. The reaction product was subsequently washed with water and distilled Example 8 381 grams (3.mols) of 2-methyl-l,3-dichloropropane, 372 grams (6.0 mols) of ethylene glycol, and 260 grams (6.5 mols) of sodium hydroxide were mixed together and gradually warmed from 30 C. up to 118 C. over a period of 55 minutes, and thereafter maintained at a temperature ranging between and C. for a period of 1 hour and 5 minutes.- The reaction mixture was thereafter washed with water to remove sodium chloride, and the wash water so obtained steamdistilled to recover small portions of products dis- (2.5 mols) of cyclo-m solved therein. The oily steam distillate and 40 grams of a higher boiling fraction comprising the dl- (hydroxy-ethyl) ether of 2-methylpropandiol-1,3, and other complex reaction products. This high boiling fraction had a specific gravity of approximately 1.07 at 20/4 C.

Example 9 127 grams (1 mol) ot 2-methyl-L3-dichloro- .'p'ropane; 108 grams (1 mol) of benzyl alcohol;

and 40 grams (1 mol) of sodium hydroxide were reacted together at a temperature of 100 to 105 C. for 8 hours. The reaction product was thereafter washed with water, dried, and Iractionally 75 distilled, whereby there was obtained 83.6 grams (0.169 .mol) of the benzyl ether of 2-methyl-3- chloro-propanol-l, which boils at 110-ll2- C. at 5. millimeters pressure, and has a specific gravity of 1.087 at 20l4 0.; and 23 grams (0.09 mol) of the di-benzyl ether of 2-methyl-propandiol-1, 3, a compound boiling at 1'70-1'72 C. at 2.5 millimeters pressure, and having a specific gravity of 1.046 at 20l4 C. Apprmdmately 19.3 grams of the benzyl ether of 2-.methyl-3-hydroxy-propenel was obtained along with 68 grams (0.535 mol) of unreacted 2-methyl-1,3-dlchloro-propane as a constantboiling mixture.

Other alcohols such as ethyl alcohol, amyl alcohol, octyl alcohol, propylene glycol, phenylethyl alcohol, etc., may be reacted with Z-methyl- 1,3-dichlor0-propane in a similar manner to produce compounds such as the ethyl ether of. 2-

methyl-(i-chloro-propanol; the di-amyl ether of 2-m.ethyl-propandiol-l,3; the octyl ether of 2- methyl-3-hydroxy-propene-1; the 2-hydroxypropyl ether of 2-methyl-S-chloro-propanol-1; the di- -(phenylethyl) ether of 2-methyl-propandiol -1,3; etc. Other alkaline materials such as sodium carbonate, potassium hydroxide, sodium alcoholate, etc., may be substituted for sodium hydroxide in the process.

' Compounds with which this application is particularly concerned have the following formula R-O-GHa-GH-CHaO-R wherein each R-represents a group selected from of the reaction mixture, and having the formula the class consisting of the alkyl, aralkyl, cycloalkyl, andhydroxyalkyl radicals.

This application is a division of a co-pending applicationserial No. 111 ,906, filed November 20.

Other modes of applying the principle of the invention may be employed instead of those'explained. change being made as regards the method or compounds herein disclosed, provided the steps or compounds stated by any of the following claims orthe equivalent of such stated steps or compounds'be employed.

We therefore-particularly point out and distinctly claim as our invention:

1. A compound obtained by the reaction of 2- methyl-i,3-dichloro-propane with an alcohol and a basic alkali metal compound at'a temperature between C. andthe decomposition temperature wherein each R represents a grand selected from the class consisting of the alkyl, aralkyl, cycloalkyl, and hydroxyalkyl radicals.

2. An ether compound having the formula ao-cm- H--OHr-O-R wherein each R represents a group selected from compound.

the class consisting of the alkyL. aralkyl, cycloalkyl, and hydroxalkyl radicals. 3. An ether compound having the formula R-O-OHr-OH-OHr-O-Ji wherein each It represents an alkyl radical.

4. An other compound having the formula R0-0Hr-OH--OH|0-R H: l V wherein each R represents a normal alkyl radical. 5. Liquid ether compounds having the formula R-o-'-orrron-oHro-R H: v wherein each It represents an alkyl group'containing from 1 to 8 carbon atoms.

6. A (ll-propyl ether of 2-methyl-propandiol-. 1,3.

'7. Di-normal-propyl ether of Z-methyl-propan- (1101-13.

8. Di-normal-butyl ether of 2-methy1-propandlol-l,3. v

9. Di-henzyl-ether of 2-methyl-propandio1-L3. 10. A method for the preparation of organic other products having the formula wherein each R. represents a group selected from the class consisting of the alkyl, aralkyl, cycloalkyl, and hydroxyalkyl radicals which comprises reacting Z-methyl-1,3-dichloropropane with an alcohol in the presence of a basic alkali metal 11. A method for the preparation of organic other products having the formula prises reacting z-methyl-lfi-dichloro-propane with a propyl alcohol in the presence of a basic alkali metal compound.

GERALD H. COLEMAN. GARNET! V. MOORE. 

